Synthesis of crystalline ZSM-35

ABSTRACT

This invention relates to a new form of crystalline material identified as having the structure of ZSM-35, to a new and useful method for synthesizing said crystalline material using 1,4-diaminocyclohexane as directing agent, and to use of said crystalline material prepared in accordance herewith as a catalyst for organic compound, e.g., hydrocarbon compound, conversion.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a new and useful method for synthesizing ahighly siliceous form of crystalline ferrierite-type material identifiedas ZSM-35, the new ZSM-35 synthesized, and use of the crystallinematerial synthesized in accordance herewith as a catalyst component fororganic compound, e.g., hydrocarbon compound, conversion.

More particularly, this invention relates to a method for preparing thecrystalline ZSM-35 structure whereby synthesis is facilitated andreproducible and the product exhibits high purity and catalytic utility.

2. Discussion of the Prior Art

Ferrierite is a naturally occurring zeolite with an intersecting 10-ringby 8-ring structure. ZSM-35 is shown to be synthesized from reactionmixtures containing ethylene diamine or pyrrolidine directing agent inU.S. Pat. Nos. 4,016,245 and 4,107,195. Synthetic ferrierite is directedfrom a certain reaction mixture in U.S. Pat. No. 4,000,248 containingN-methylpyridinium; and another reaction mixture containing choline inU.S. Pat. No. 4,046,859. Piperidine is the directing agent in U.S. Pat.No. 4,251,499 for synthetic ferrierite. U.S. Pat. Nos. 4,323,481 and4,390,457 teach synthesis of ferrierite from reaction mixturescomprising directing agents of 2,4-pentanedione and 2-aminopyridine,respectively. U.S. Pat. No. 4,377,502 shows morpholine or dioxane usedas directing agent for ferrierite synthesis. U.S Pat. No. 4,584,286teaches a method for synthesis of ZSM-35 from a reaction mixturecomprising bis(N-methylpyridyl) ethylinium as directing agent. Both U.S.Pat. Nos. 4,578,259 and 4,695,440 show use of pyridine plus ethyleneglycol as directing agent for synthetic ferrierite; and both U.S. Pat.Nos. 4,721,607 and 4,855,270 show use of pyridine plus ethylene diamineand ethanol as directing agent for synthetic ferrierite. U.S. Pat. No.4,925,548 teaches synthesis of ZSM-35 with hexamethyleneimine directingagent.

The above disclosures are incorporated herein by reference as to ZSM-35,synthetic ferrierite and their synthesis.

Various organic directing agents are taught for synthesis of variouscrystalline materials. For example, U.S. Pat. No. 4,139,600 teaches amethod for synthesis of zeolite ZSM-5 from a reaction mixturecomprising, as a directing agent, an alkyldiamine. U.S. Pat. No.4,296,083 claims synthesizing zeolites characterized by a ConstraintIndex of 1 to 12 and an alumina/silica mole ratio of not greater than0.083 from a specified reaction mixture containing an organicnitrogen-containing cation provided by an amine identified as beingselected from the group consisting of triethylamine, trimethylamine,tripropylamine, ethylenediamine, propanediamine, butanediamine,pentanediamine, hexanediamine, methylamine, ethylamine, propylamine,butylamine, dimethylamine, diethylamine, dipropylamine, benzylamine,aniline, pyridine, piperidine and pyrrolidine.

Piperidine is disclosed as an organic directing agent for mordenitesynthesis by P. A. Jacobs and J. A. Martens, STUDIES OF SURFACE SCIENCEAND CATALYSIS, 33, 12 (1987); and 2-amino-pyridine is taught for thispurpose in U.S. Pat. No. 4,390,457. Tetra-n-propylammonium salts aretaught to be mordenite directing agents in U.S. Pat. Nos. 4,707,345 and4,788,380.

U.S. Pat. No. 4,151,189 claims a method for synthesizing zeolites ZSM-5,ZSM-12, ZSM-35 and ZSM-38 containing an organic nitrogen cation from aspecified reaction mixture containing a primary amine having 2 to 9carbon atoms as a directing agent. U.S. Pat. No. 4,341,748 showssynthesis of ZSM-5 structure from reaction mixtures comprising ethanol,ZSM-5 seeds, ethanol and seeds, ethanol and ammonium hydroxide, andethanol, ammonium hydroxide and ZSM-5 seeds. U.S. Pat. No. 4,100,262teaches synthesis of ZSM-5 from a reaction mixture comprising atetraalkylammonium source and a tetraureacobalt (II) complex.

Lok et al. (3 Zeolites, 282-291 (1983)) teach numerous organic compoundswhich act as directing agents for synthesis of various crystallinematerials, such as, for example, ZSM-5, ZSM-11, ZSM-12, ZSM-20, ZSM-35,ZSM-48, AlPO₄ -5, AlPO₄ -8, AlPO₄ -20 and others. The article does notshow the presently required organic for synthesis of ZSM-35. The articledoes show that cyclohexylamine, N-methylcyclohexylamine,dicyclohexylamine and ethyl-n-butylamine may direct synthesis of AlPO₄-5 (U.S. Pat. No 4,310,440).

The zeolitic compositions labeled "PSH-3" in U.S. Pat. No. 4,439,409 aresynthesized from reaction mixtures containing hexamethyleneimine asdirecting agent. U.S. Pat. No. 4,954,325 utilizes hexamethyleneimine inanother reaction mixture to direct synthesis of MCM-22. That organic isused in U.S. Pat. No. 4,981,663 for synthesis of yet another crystallinestructure labelled MCM-35. As mentioned above, ZSM-35 is directed bythis same compound in U.S. Pat. No. 4,925,548.

Other publications teaching various organic directing agents forsynthesis of various crystalline materials include, for example, U.S.Pat. No. 4,592,902, teaching use of an alkyltropinium directing agent,alkyl being of 2 to 5 carbon atoms, for synthesis of ZSM-5; U.S. Pat.No. 4,640,829, teaching use of dibenzyldimethylammonium directing agentfor synthesis of ZSM-50; U.S. Pat. No. 4,637,923, teaching use of (CH₃)₂(C₂ H₅)N⁺ (CH₂)₄ N⁺ (C₂ H₅)(CH₃)₂ directing agent for synthesis ofanother novel zeolite; U.S. Pat. No. 4,585,747, teaching use of bis(N-methylpyridyl) ethylinium directing agent for synthesis of ZSM-48;U.S. Pat. No. 4,585,746, teaching use of bis (N-methylpyridyl)ethylinium directing agent for synthesis of ZSM-12; U.S. Pat. No.4,584,286, mentioned above, teaching use of bis (N-methylpyridyl)ethylinium directing agent for synthesis of ZSM-35; U.S. Pat. No.4,568,654, teaching use of cobalticinium, dimethylpiperidinium,trimethylene bis trimethylammonium or tetramethylpiperazinium directingagents for synthesis of ZSM-51; U.S. Pat. No. 4,559,213, teaching use ofDABCO-C₄₋₁₀ -diquat directing agent for synthesis of ZSM-12; U.S. Pat.No. 4,482,531, teaching synthesis of ZSM-12 with a DABCO-C_(n) -diquat,n being 4,5,6 or 10, directing agent; and U.S. Pat. No. 4,539,193,teaching use of bis (dimethylpiperidinium) trimethylene directing agentfor synthesis of ZSM-12.

Various diquaternary ammonium compounds have been identified asdirecting agents for a particular assortment of crystalline materials.For instance, U.S. Pat. Nos. 4,490,342 and 4,619,820 show synthesis ofZSM-23 from a reaction mixture containing the organic of U.S. Pat. No.4,531,012, i.e., (CH₃)₃ N⁺ (R)N⁺ (CH₃)₃, where R is a saturated orunsaturated hydrocarbon having 7 carbon atoms. U.S. Pat. No. 4,665,250teaches the use of linear diquaternary ammonium compounds of thestructure (CH₃)₃ N³⁰ (CH₂)_(m) N⁺ (CH₃)₃, m being 5, 6, 8, 9 or 10, forsynthesis of ZSM-48. U.S. Pat. No. 4,623,527 teaches numerousdiquaternary ammonium compounds and shows use of (CH₃)₃ N⁺ (CH₂)₇ N⁺(CH₃)₃ directing agent for synthesis of MCM-10.

U.S. Pat. No. 4,632,815 teaches numerous diquaternary ammonium compoundsand shows use of (CH₃)₃ N⁺ (CH₂)₄ N⁺ (CH₃)₃ to direct synthesis of aSilica-X structure type. U.S. Pat. No. 4,585,639 teaches use of thediquaternary (C₂ H₅)(CH₃)₂ N⁺ (CH₂)_(4or6) N⁺ (CH₃)₂ (C₂ H₅) asdirecting agent for synthesis of ZSM-12. Synthesis of ZSM-5 is directedby the diquaternary (alkyl)₃ N⁺ (CH₂)₆ N⁺ (alkyl)₃, alkyl being propylor butyl, in U.S. Pat. No. 4,585,638.

EPA 42,226 and U.S. Pat. No. 4,537,754 teach existence of numerousdiquaternary ammonium compounds, but show use of (CH₃)₃ N⁺ (CH₂)₆ N⁺(CH₃)₃ as directing agent for synthesis of EU-1. EPA 51,318 teaches useof the same diquaternary for synthesis of TPZ-3. It is noted that EU-1,TPZ-3 and ZSM-50 (synthesized with dibenzyldimethylammonium directingagent) have the same structure.

Applicants know of no prior art method for preparing a highly siliceouscrystalline ferrierite-type structure identified as ZSM-35 utilizing thepresent method.

SUMMARY OF THE INVENTION

An economical and reproducible method for preparing a crystallinematerial identified as ZSM-35 exhibiting high purity, catalytic activityand other valuable properties is provided. The method comprises forminga reaction mixture hydrogel containing sources of alkali or alkalineearth metal (M) cations; an oxide of trivalent element (X), e.g.,aluminum, boron, iron, gallium, indium and mixtures thereof; an oxide oftetravalent element (Y), e.g., silicon, germanium, tin and mixturesthereof; a directing agent (R) of 1,4-diaminocyclohexane; and water,said reaction mixture having a composition in terms of mole ratios,within the following ranges:

    ______________________________________                                        Reactants      Useful    Preferred                                            ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                     1 to 100 10 to 50                                             H.sub.2 O/YO.sub.2                                                                            10 to 100                                                                              15 to 50                                             OH.sup.- /YO.sub.2                                                                             0 to 0.25                                                                               0 to 0.1                                           M/YO.sub.2       0 to 2.0                                                                              0.10 to 1.0                                          R/YO.sub.2     0.1 to 2.0                                                                              0.14 to 1.0                                          ______________________________________                                    

The method further comprises maintaining the reaction mixture untilcrystals of ZSM-35 structure are formed. Reaction conditions requiredconsist of heating the foregoing reaction mixture to a temperature offrom about 100° C. to about 200° C. for a period of time of from about10 hours to about 10 days. A more preferred temperature range is fromabout 130° C. to about 180° C. with the amount of time at a temperaturein such range being from about 2 days to about 8 days. The solid productcomprising ZSM-35 crystals is recovered from the reaction medium, as bycooling the whole to room temperature, filtering and water washing.

EMBODIMENTS

The particular effectiveness of the presently required organic directingagent, i.e., 1,4-diaminocyclohexane, when compared with other directingagents, such as those identified above, for the present synthesis isbelieved due to its ability to function as a template in the nucleationand growth of ZSM-35 crystals from the above low YO₂, e.g., SiO₂, lowalkalinity, e.g., low OH⁻ /YO₂, reaction mixture. This is true eventhough no predigestion of the gel is required prior to crystallization.This different organic agent functions in this fashion in the reactionmixture having the above described composition and under the abovedescribed conditions of temperature and time. The reaction mixturerequired for this invention is X-rich, e.g., aluminum-rich, with a YO₂/X₂ O₃ molar ratio of from about 1/1 to about 100/1, preferably fromabout 10/1 to about 50/1, most preferably from about 10/1 to about 30/1.

It should be noted that the ratio of components of the reaction mixturerequired herein are critical to achieve maximum effectiveness. Forinstance, if the YO₂ / X₂ O₃ ratio is above about 70, something otherthan ZSM-35 will form. In general, with higher YO₂ /X_(x) O₃ ratios inthe reaction mixture, crystallization of layered material increases andZSM-35 decreases. Further, at YO₂ /X₂ O₃ molar ratios less than about70, the R/YO₂ mole ratio minimum for most successful ZSM-35 synthesis isabout 0.1/1. When this ratio drops below about 0.14 at the YO₂ /X₂ O₃ratios of, for example, 20 or less, mixtures of layered and amorphousmaterials comprise the product. Still further, for most effectivesynthesis of ZSM-35 by this method, the OH⁻ /YO₂ ratio should be greaterthan 0.

The synthesis of the present invention is facilitated when the reactionmixture comprises seed crystals, such as those having the structure ofZSM-35. The use of at least 0.01%, preferably about 0.10%, and even morepreferably about 1% seed crystals (based on total weight) of crystallinematerial will be useful.

The reaction mixture composition for the synthesis of ZSM-35 crystalshereby can be prepared utilizing materials which can supply theappropriate oxide. The useful sources of X₂ O₃, e.g., aluminum oxide,iron oxide and/or boron oxide, include, as non-limiting examples, anyknown form of such oxide, e.g., aluminum oxide or hydroxide, organic orinorganic salt or compound, e.g., alumina, aluminates and borates. Theuseful sources of YO₂, e.g., silicon oxide, include, as non-limitingexamples, known forms of such oxide, e.g., silicic acid or silicondioxide, alkoxy- or other compounds of silicon, including silica gel andsilica hydrosol.

It will be understood that each oxide component utilized in the reactionmixture for this synthesis can be supplied by one or more essentialreactants and they can be mixed together in any order. For example, anyoxide can be supplied by an aqueous solution. The reaction mixture canbe prepared either batchwise or continuously. Crystal size andcrystallization time for the product composition comprising the ZSM-35crystals will vary with the exact nature of the reaction mixtureemployed within the above limitations.

The 1,4-diaminocyclohexane directing agent for use herein can be eitherin the trans- or cis- form or mixtures thereof.

The ZSM-35 crystal composition prepared hereby has a characteristicX-ray diffraction pattern, including values substantially as set forthin Table 1, hereinafter.

                  TABLE 1                                                         ______________________________________                                        Interplanar d-Spacing, (A)                                                                       Relative Intensity (I/I.sub.o)                             ______________________________________                                        11.40 ± 0.30    w                                                          9.55 ± 0.20     m-s                                                        7.07 ± 0.05     w-m                                                        6.95 ± 0.05     w-m                                                        6.60 ± 0.05     w-m                                                        5.79 ± 0.06     w                                                          5.69 ± 0.05     w                                                          4.00 ± 0.08     s twin peaks                                               3.95 ± 0.02     m*                                                         3.87 ± 0.03     w                                                          3.78 ± 0.03     m-s                                                        3.68 ± 0.06     w                                                          3.55 ± 0.03     s-vs                                                       3.48 ± 0.03     s-vs                                                       3.40 ± 0.05     w                                                          3.31 ± 0.03     w-m                                                        3.15 ± 0.03     w-m                                                        3.07 ± 0.03     w                                                          2.89 ± 0.04     w                                                          ______________________________________                                         *Not fully resolved                                                      

These X-ray diffraction data were collected with a Rigaku diffractionsystem, equipped with a graphite diffracted beam monochromator andscintillation counter, using copper K-alpha radiation. The diffractiondata were recorded by step-scanning at 0.02 degrees of two-theta, wheretheta is the Bragg angle, and a counting time of 1 second for each step.The interplanar spacings, d's, were calculated in Angstrom units (A),and the relative intensities of the lines, I/I_(o), where I_(o) isone-hundredth of the intensity of the strongest line, above background,were derived with the use of a profile fitting routine (or secondderivative algorithm). The intensities are uncorrected for Lorentz andpolarization effects. The relative intensities are given in terms of thesymbols vs=very strong (75-100), s=strong (50-74), m=medium (25-49) andw=weak (0-24). It should be understood that diffraction data listed forthis sample as single lines may consist of multiple overlapping lineswhich under certain conditions, such as differences in crystallite sizesor very high experimental resolution or crystallographic change, mayappear as resolved or partially resolved lines. Typically,crystallographic changes can include minor changes in unit cellparameters and/or a change in crystal symmetry, without a change intopology of the structure. These minor effects, including changes inrelative intensities, can also occur as a result of differences incation content, framework composition, nature and degree of porefilling, and thermal and/or hydrothermal history.

The crystalline ZSM-35 prepared hereby has a composition involving themolar relationship:

    X.sub.2 O.sub.3 :(y)YO.sub.2

wherein X is a trivalent element, such as aluminum, boron, iron, indiumand/or gallium, preferably aluminum; Y is a tetravalent element, such assilicon, tin and/or germanium, preferably silicon; and y is from about 1to about 100, usually from about 10 to about 50, more usually from about10 to about 30. In the as-synthesized form, the crystalline material hasa formula, on an anhydrous basis and in terms of moles of oxides per ymoles of YO₂, as follows:

    (0.4 to 0.6)M.sub.2 O:(0.2 to 0.6)R.sub.2 O:X.sub.2 O.sub.3 :(y)YO.sub.2

wherein M and R are as defined above. The M and R components areassociated with the material as a result of their presence duringcrystallization, and are easily removed by post-crystallization methodshereinafter more particularly described.

Synthetic ZSM-35 crystals prepared in accordance herewith can be usedeither in the as-synthesized form, the hydrogen form or anotherunivalent or multivalent cationic form. It can also be used in intimatecombination with a hydrogenating component such as tungsten, vanadium,molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noblemetal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed. Such components can beexchanged into the composition, impregnated therein or physicallyintimately admixed therewith. Such components can be impregnated in oron to the ZSM-35 such as, for example, by, in the case of platinum,treating the material with a platinum metal-containing ion. Suitableplatinum compounds for this purpose include chloroplatinic acid,platinous chloride and various compounds containing the platinum aminecomplex. Combinations of metals and methods for their introduction canalso be used.

Synthetic ZSM-35 crystals, when employed either as an adsorbent or as acatalyst in a hydrocarbon conversion process, should be dehydrated atleast partially. This can be done by heating to a temperature in therange of from about 65° C. to about 315° C. in an inert atmosphere, suchas air, nitrogen, etc. and at atmospheric or subatmospheric pressuresfor between 1 and 48 hours. Dehydration can be performed at lowertemperature merely by placing the zeolite in a vacuum, but a longer timeis required to obtain a particular degree of dehydration. The thermaldecomposition product of the newly synthesized ZSM-35 can be prepared byheating same at a temperature of from about 200° C. to about 550° C. forfrom 1 hour to about 48 hours. The original cations, e.g., alkali oralkaline earth metal, of the as-synthesized material can be replaced inaccordance with techniques well known in the art, at least in part, byion exchange with other cations. Preferred replacing cations includemetal ions, hydrogen ions, hydrogen precursor, e.g., ammonium, ions andmixtures thereof. Particularly preferred cations are those which renderthe material catalytically active, especially for certain hydrocarbonconversion reactions. These include hydrogen, rare earth metals andmetals of Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB and VIII of thePeriodic Table of the Elements, especially gallium, indium and tin.

Typical ion exchange technique would be to contact the synthetic ZSM-35material with a salt of the desired replacing cation or cations.Examples of such salts include the halides, e.g., chlorides, nitratesand sulfates.

Representative ion exchange techniques are disclosed in a wide varietyof patents including U.S. Pat. Nos 3,140,249; 3,140,251; and 3,140,253.

Following contact with the salt solution of the desired replacingcation, the ZSM-35 is then preferably washed with water and dried at atemperature ranging from 65° C. to about 315° C. and thereafter may becalcined in air or other inert gas at temperatures ranging from about200° C. to about 550° C. for periods of time ranging from 1 to 48 hoursor more to produce a catalytically-active thermal decomposition productthereof.

The crystalline ZSM-35 prepared by the instant invention is formed in awide variety of particle sizes. Generally speaking, the particles can bein the form of a powder, a granule, or a molded product, such asextrudate having particle size sufficient to pass through a 2 mesh(Tyler) screen and be retained on a 400 mesh (Tyler) screen. In caseswhere the catalyst is molded, such as by extrusion, the crystallinematerial can be extruded before drying or dried or partially dried andthen extruded.

In the case of many catalysts, it is desired to incorporate the crystalshereby prepared with another material resistant to the temperatures andother conditions employed in certain organic conversion processes. Suchmatrix materials include active and inactive materials and synthetic ornaturally occurring zeolites as well as inorganic materials such asclays, silica and/or metal oxides, e.g., alumina, titania and/orzirconia. The latter may be either naturally occurring or in the form ofgelatinous precipitates, sols or gels including mixtures of silica andmetal oxides. Use of a material in conjuction with the ZSM-35, i.e.,combined therewith, which is active, may enhance the conversion and/orselectivity of the catalyst in certain organic conversion processes.Inactive materials suitably serve as diluents to control the amount ofconversion in a given process so that products can be obtainedeconomically and orderly without employing other means for controllingthe rate or reaction. Frequently, crystalline catalytic materials havebeen incorporated into naturally occurring clays, e.g., bentonite andkaolin. These materials, i.e., clays, oxides, etc., function, in part,as binders for the catalyst. It is desirable to provide a catalysthaving good crush strength because in a petroleum refinery the catalystis often subjected to rough handling, which tends to break the catalystdown into powder-like materials which cause problems in processing.

Naturally occurring clays which can be composited with the herebysynthesized crystalline material include the montmorillonite and kaolinfamilies which include the subbentonites, and the kaolins commonly knownas Dixie, McNamee, Georgia and Florida clays, or others in which themain mineral constituent is halloysite, kaolinite, dickite, nacrite oranauxite. Such clays can be used in the raw state as originally mined orinitially subjected to calcination, acid treatment or chemicalmodification.

In addition to the foregoing materials, the present crystals can becomposited with a porous matrix material such as silica-alumina,silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia,silica-titania, as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesiaand silica-magnesia-zirconia. The matrix can be in the form of a cogel.A mixture of these components could also be used.

The relative proportions of finely divided crystalline material andmatrix vary widely with the crystalline material content ranging fromabout 1 to about 90 percent by weight, and more usually in the range ofabout 2 to about 50 percent by weight of the composite.

Employing a catalytically active form of the catalyst of this inventionwhich may contain additional hydrogenation components, reforming stockscan be reformed employing a temperature between about 370° C. and about540° C. The pressure can be between about 100 psig and about 1000 psig,but it is preferably between about 200 psig and about 700 psig. Theliquid hourly space velocity is generally between about 0.1 and about 10hr⁻¹, preferably between about 0.5 and about 4 hr⁻¹, and the hydrogen tohydrocarbon mole ratio is generally between about 1 and about 20,preferably between about 4 and about 12.

The catalyst can also be used for hydroisomerization of normalparaffins, when provided with a hydrogenation component, e.g., platinum.Hydroisomerization is carried out at a temperature between about 90° C.and 375° C., preferably about 145° C. to about 290° C., with a liquidhourly space velocity between about 0.01 and about 2 hr⁻¹, preferablybetween about 0.25 and about 0.50 hr⁻¹, employing hydrogen such that thehydrogen to hydrocarbon mole ratio is between about 1:1 and about 5:1.

The catalyst can also be used for reducing the pour point of gas oils.This reaction may be conducted at a liquid hourly space velocity betweenabout 10 and about 30 hr⁻¹ and at a temperature between about 400° C.and about 540° C.

Other reactions which can be accomplished employing the catalyst of thisinvention containing a metal, e.g., platinum, includehydrogenation-dehydrogenation reactions and desulfurization reactions.

In order to more fully illustrate the nature of the invention and themanner of practicing same, the following examples are presented. In theexamples, whenever adsorption data are set forth for comparison ofsorptive capacities for water, cyclohexane and n-hexane, they aredetermined as follows:

A weighed sample of the calcined adsorbant is contacted with the desiredpure adsorbate vapor in an adsorption chamber, evacuated to 1 mm andcontacted with 12 mm Hg of water vapor or 20 mm Hg of n-hexane, orcyclohexane vapor, pressures less than the vapor-liquid equilibriumpressure of the respective adsorbate at room temperature. The pressureis kept constant (within about ±0.5 mm) by addition of absorbate vaporcontrolled by a manostat during the adsorption period, which does notexceed about 8 hours. As adsorbate is adsorbed by the sorbant material,the decrease in pressure causes the manostat to open a valve whichadmits more adsorbate vapor to the chamber to restore the above controlpressures. Sorption is complete when the pressure change is notsufficient to activate the manostat. The increase in weight iscalculated as the adsorption capacity of the sample in g/100 g ofcalcined adsorbant.

When Alpha Value is examined, it is noted that the Alpha Value is anapproximate indication of the catalytic cracking activity of thecatalyst compared to a standard catalyst and it gives the relative rateconstant (rate of normal hexane conversion per volume of catalyst perunit time). It is based on the activity of silica-alumina crackingcatalyst taken as an Alpha of 1 (Rate Constant=0.016 sec⁻¹). The AlphaTest is described in U.S. Pat. No. 3,354,078; in the Journal ofCatalysis, Vol. 4, p. 527 (1965); Vol. 6, p. 278 (1966); and Vol. 61, p.395 (1980), each incorporated herein by reference as to thatdescription. The experimental conditions of the test used herein includea constant temperature of 538° C. and a variable flow rate as describedin detail in the Journal of Catalysis, Vol. 61, p. 395.

EXAMPLE 1

To water (47.2 g) was added sodium aluminate (1.445 g, technical grade,74% solids), and sodium hydroxide (0.53 g). This mixture was stirredbriefly to complete dissolution, then trans-1,4-diaminocyclohexane (2.26g) was added. To this solution was added silica (Ultrasil™, 9.12 g), andthe resulting gel was transferred to a Teflon™ liner, placed in anautoclave, pressurized (100 psig), sealed, then heated (145° C.) withstirring (˜350 rpm) for 8 days.

After cooling, the product was suction filtered, washed with water, thendried (110° C., in vacuo) to give a white powder (9.06 g). The X-raydiffraction pattern (lambda= 1.5418) of the product proved it to becrystalline ZSM-35, and is shown in Table 2.

                  TABLE 2                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        11.39           7.76     13.79                                                9.47            9.34     76.47                                                7.09            12.48    26.58                                                6.93            12.78    16.66                                                6.60            13.42    14.02                                                5.75            15.42    18.25                                                4.95            17.92    5.87                                                 4.816           18.42    7.15                                                 3.98            22.32    51.07                                                3.93            22.62    34.50                                                3.84            23.14    28.86                                                3.78            23.54    48.88                                                3.65            24.40    23.53                                                3.54            25.12    100.00                                               3.47            25.68    75.06                                                3.37            26.46    13.88                                                3.32            26.88    25.13                                                3.13            28.54    25.67                                                3.04            29.34    17.84                                                2.95            30.28    7.69                                                 2.89            30.90    8.97                                                 2.84            31.52    6.10                                                 2.70            33.12    6.92                                                 2.66            33.74    7.42                                                 ______________________________________                                    

EXAMPLE 2 (Comparative)

To water (47.2 g) was added sodium hydroxide (1.036 g). This mixture wasstirred briefly to complete dissolution, thentrans-1,4-diaminocyclohexane (5.549 g) was added. To this solution wasadded silica (Ultrasil™, 9.12 g), and the resulting gel was transferredto a Teflon™ liner, placed in an autoclave, pressurized (100 psig),sealed, then heated (145° C.) with stirring (˜350 rpm) for 8 days. Aftercooling, the product was suction filtered, washed with water, then dried(110° C., in vacuo) to give a white powder (9.06 g) which was notZSM-35. The XRD pattern (lambda=1.5406) of the product is set out inTable 3.

                  TABLE 3                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        12.20           7.24     100.00                                               10.65           8.30     0.40                                                 9.22            9.59     0.95                                                 7.00            12.63    0.58                                                 6.14            14.41    0.95                                                 5.28            16.76    2.45                                                 4.18            21.25    0.77                                                 4.12            21.54    4.62                                                 4.03            22.02    0.95                                                 3.68            24.14    3.54                                                 3.61            24.61    5.15                                                 3.49            25.50    1.32                                                 3.32            26.87    4.17                                                 3.20            27.87    0.98                                                 3.10            28.72    1.03                                                 2.74            32.66    1.19                                                 ______________________________________                                    

Calculation of this product (350° C., 2 hrs.) caused loss of this XRDpattern to a dense phase material.

EXAMPLE 3

To water (47.2 g) was added sodium aluminate (1.433 g, technical grade,74% solids) and sodium hydroxide (0.545 g). This mixture was stirredbriefly to complete dissolution, then trans-1,4-diaminocyclohexane(5.531 g) was added. To this solution was added silica (Ultrasil™, 9.14g), and the resulting gel was transferred to a Teflon™ liner, placed inan autoclave, pressurized (100 psig), sealed, then heated (145° C.) withstirring (.sup.˜ 350 rpm) for 8 days. After cooling, the product wassuction filtered, washed with water, then dried (110° C., in vacuo) togive a mixture of ZSM-35 and layered material as a white powder (12.364g). The XRD pattern (lambda=1.5418) of the product is set out in Table4.

                  TABLE 4                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        12.45           7.10     29.99                                                11.19           7.90     12.49                                                9.31            9.50     73.44                                                7.02            12.62    25.15                                                6.55            13.52    13.46                                                5.70            15.54    19.70                                                5.38            16.48    7.83                                                 4.92            18.04    6.68                                                 4.77            18.60    7.39                                                 4.68            18.96    5.45                                                 4.41            20.14    5.10                                                 4.16            21.34    20.58                                                3.95            22.50    52.77                                                3.89            22.86    34.56                                                3.75            23.72    51.28                                                3.62            24.60    35.53                                                3.52            24.32    100.00                                               3.45            25.84    81.00                                                3.34            26.70    15.74                                                3.30            27.02    24.19                                                3.19            27.96    7.12                                                 3.11            28.70    27.70                                                3.02            29.56    21.28                                                2.94            30.46    8.18                                                 2.87            31.16    10.29                                                2.82            31.78    7.12                                                 2.76            32.48    5.28                                                 2.69            33.32    7.83                                                 2.64            33.96    7.30                                                 2.57            34.90    7.39                                                 ______________________________________                                    

The as-synthesized product (1 g) was calcined (538° C., 3 hrs.) to givea product which gave the pattern set out in Table 5.

                  TABLE 5                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        11.28           7.84     5.97                                                 9.43            9.38     100.00                                               6.94            12.76    36.61                                                6.58            13.46    22.42                                                5.64            15.72    18.11                                                5.38            16.46    4.72                                                 4.74            18.74    11.02                                                4.52            19.64    5.07                                                 4.38            20.28    7.42                                                 4.18            21.24    5.13                                                 3.96            22.44    44.09                                                3.83            23.22    23.51                                                3.76            23.68    42.56                                                3.64            24.44    26.95                                                3.52            25.28    67.23                                                3.46            25.78    54.23                                                3.36            26.52    17.88                                                3.30            27.02    18.86                                                3.12            28.58    25.61                                                3.04            29.42    15.36                                                2.94            30.42    11.09                                                2.88            31.04    9.37                                                 2.84            31.56    5.78                                                 2.80            31.96    5.16                                                 2.70            33.14    6.87                                                 ______________________________________                                    

These data illustrate that the product is a mixture, and that thecomponent giving rise to the lowest-angle peak is unstable to thesecalcination conditions. The ZSM-35 component is stable.

EXAMPLE 4

To water (47.2 g) was added sodium aluminate (1.071 g, technical grade,74% solids) and sodium hydroxide (0.545 g). This mixture was stirredbriefly to complete dissolution, then trans-1,4-diaminocyclohexane(5.536 g) was added. To this solution was added silica (Ultrasil™, 9.13g), and the resulting gel was transferred to a Teflon™ liner, placed inan autoclave, pressurized (100 psig), sealed, then heated (145° C.) withstirring (.sup.˜ 350 rpm) for 8 days. After cooling, the product wassuction filtered, washed with water, then dried (110° C., in vacuo) togive ZSM-35 as a white powder (8.877 g). The XRD pattern (lambda-321.5418) of the product is set out in Table 6.

                  TABLE 6                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        12.45           7.10     45.66                                                11.22           7.88     14.93                                                9.41            9.40     86.35                                                7.05            12.56    24.34                                                6.58            13.46    13.29                                                5.73            15.46    19.31                                                5.34            16.60    8.69                                                 4.96            17.90    6.37                                                 4.95            17.92    6.37                                                 4.80            18.48    8.25                                                 4.16            21.36    25.78                                                3.98            22.36    58.78                                                3.77            23.58    53.52                                                3.64            24.44    36.08                                                3.53            25.22    100.00                                               3.46            25.76    76.43                                                3.36            26.52    16.65                                                3.31            26.92    24.71                                                3.24            27.52    7.38                                                 3.12            28.60    26.96                                                3.04            29.42    21.43                                                2.94            30.44    8.83                                                 2.88            31.00    10.73                                                2.83            31.58    7.09                                                 2.75            32.54    5.52                                                 2.70            33.20    8.01                                                 2.64            33.96    8.34                                                 ______________________________________                                    

These data indicate that increasing the SiO₂ /Al₂ O₃ in the preparationgel serves to increase the thermally unstable low-angle component in theproduct mixture.

EXAMPLE 5

To water (47.2 g) was added sodium aluminate (0.506 g, technical grade,74% solids) and sodium hydroxide (0.535 g). This mixture was stirredbriefly to complete dissolution, then trans-1,4-diaminocyclohexane(5.537 g) was added. To this solution was added silica (Ultrasil™, 9.14g), and the resulting gel was transferred to a Teflon™ liner, placed inan autoclave, pressurized (100 psig), sealed, then heated (145° C.) withstirring (.sup.˜ 350 rpm) for 8 days. After cooling, the product wassuction filtered, washed with water, then dried (110° C., in vacuo) togive a white powder (7.598 g). The XRD pattern (lambda=1.5418) of theproduct is set out in Table 7.

                  TABLE 7                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        19.72           4.48     13.05                                                12.38           7.14     88.58                                                10.92           8.10     8.11                                                 9.74            9.08     19.16                                                7.04            12.58    10.91                                                6.56            13.50    6.58                                                 5.79            15.30    5.02                                                 5.65            15.68    5.37                                                 5.36            16.54    10.41                                                4.93            17.98    5.85                                                 4.43            20.06    6.38                                                 4.24            20.96    31.54                                                4.17            21.32    47.32                                                4.08            21.80    23.04                                                3.97            22.38    21.66                                                3.80            23.44    16.70                                                3.65            24.40    25.43                                                3.64            24.42    25.43                                                3.52            25.24    37.02                                                3.47            25.68    24.42                                                3.34            26.72    100.00                                               3.21            27.76    11.08                                                3.13            28.54    12.98                                                3.06            29.18    8.13                                                 3.03            29.46    7.72                                                 2.96            30.14    6.82                                                 2.91            30.72    6.96                                                 2.88            31.00    7.00                                                 2.75            32.54    6.04                                                 ______________________________________                                    

These data show that at SiO₂ /Al₂ O₃ =5953 the thermally unstablelow-angle component dominates the product mixture along with some denserphase material. The peaks at d-spacing=4.238 and 3.336 are identified asalpha-quartz.

EXAMPLE 6

To water (47.2 g) was added sodium aluminate (0.506 g, technical grade,74% solids) and sodium hydroxide (0.708 g). This mixture was stirredbriefly to complete dissolution, then trans-1,4-diaminocyclohexane(5.537 g) was added. To this solution was added silica (Ultrasil™, 9.14g), and the resulting gel was transferred to a Teflon™ liner, placed inan autoclave, pressurized (100 psig), sealed, then heated (145° C.) withstirring (.sup.˜ 350 rpm) for 8 days. After cooling, the product wassuction filtered, washed with water, then dried (110° C., in vacuo) togive a white powder (8.850 g). The XRD pattern (lambda=1.5418) of theproduct is set out in TABLE 8.

                  TABLE 8                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        12.42           7.12     54.73                                                11.28           7.84     5.77                                                 9.55            9.26     15.19                                                7.06            12.54    7.13                                                 6.58            13.46    4.38                                                 5.72            15.48    4.93                                                 5.36            16.54    6.31                                                 4.88            18.16    9.20                                                 4.52            19.64    3.20                                                 4.41            20.14    3.81                                                 4.23            20.98    24.06                                                4.15            21.40    28.32                                                3.97            22.38    14.13                                                3.97            22.40    14.13                                                3.79            23.50    12.16                                                3.65            24.40    15.76                                                2.53            25.24    23.25                                                3.46            25.78    17.08                                                3.33            26.74    100.00                                               3.22            27.72    6.33                                                 3.12            28.58    8.44                                                 3.03            29.52    5.23                                                 2.96            30.20    4.00                                                 2.89            30.96    4.59                                                 2.75            32.56    4.25                                                 ______________________________________                                    

These data show that increasing sodium content gives similar results toExample 5, but with somewhat sharper peaks. The peaks at d-spacing=4,234 are identified as alpha-quartz.

EXAMPLE 7

To water (47.2 g) was added sodium hydroxide (1.049 g). This mixture wasstirred briefly to complete dissolution, thentrans-1,4-diaminocyclohexane (5.549 g) was added. To this solution wasadded silica (Ultrasil™, 9.13 g), and the resulting gel was transferredto a Teflon™ liner, placed in an autoclave, pressurized (100 psig),sealed, then heated (100° C.) with stirring (.sup.˜ 350 rpm) for 8 days.After cooling, the product was suction filtered, washed with water, thendried (110° C., in vacuo) to give a white powder (6.823 g) The XRDpattern (lambda=1.5418) of the product showed only a broad peak near2-theta=20 which indicates crystallization is largely incomplete whenthe temperature was lowered from Example 2.

EXAMPLE 8

To water (47.2 g) was added sodium aluminate (0.287 g, technical grade,74% solids) and sodium hydroxide (0.537 g). This mixture was stirredbriefly to complete dissolution, then trans-1,4-diaminocyclohexane(5.535 g) was added. To this solution was added silica (Ultrasil™, 9.13g), and the resulting gel was transferred to a Teflon™ liner, placed inan autoclave, pressurized (100 psig), sealed, then heated (145° C.) withstirring (.sup.˜ 350 rpm) for 7 days. After cooling, the product wassuction filtered, washed with water, then dried (110° C., in vacuo) togive a white powder (8.726 g). The XRD pattern (lambda=1.5418) of theproduct is set out in Table 9.

                  TABLE 9                                                         ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        21.55           4.10     16.92                                                15.45           5.72     100.00                                               13.56           6.52     17.95                                                12.42           7.12     19.45                                                11.19           7.90     14.77                                                10.05           8.80     14.11                                                9.45            9.36     12.62                                                7.72            11.46    11.76                                                5.14            17.26    23.58                                                4.47            19.88    20.68                                                4.24            20.94    31.43                                                4.11            21.62    68.17                                                3.86            23.04    28.99                                                3.68            24.18    23.36                                                3.56            24.74    24.52                                                3.49            25.52    61.72                                                3.35            26.62    47.10                                                3.19            28.00    38.60                                                3.09            28.90    12.08                                                3.00            29.82    10.00                                                2.84            31.56    10.36                                                ______________________________________                                    

EXAMPLE 9

To water (47.2 g) was added sodium aluminate (1.071 g, technical grade,74% solids) and sodium hydroxide (0.555 g). This mixture was stirredbriefly to complete dissolution, then trans-1,4-diaminocyclohexane(5.545 g) was added. To this solution was added silica (Ultrasil™, 9.12g), and the resulting gel was transferred to a Teflon™ liner, placed inan autoclave, pressurized (100 psig), sealed, then heated (145° C.) withstirring (.sup.˜ 350 rpm) for 6 days. After cooling, the product wassuction filtered, washed with water, then dried (110° C., in vacuo) to awhite powder (8.815 g). The XRD pattern (lambda=1.5418) of the productis set out in Table 10.

                  TABLE 10                                                        ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        11.36           7.78     11.59                                                10.43           8.48     7.55                                                 8.88            9.96     38.21                                                6.71            13.20    15.43                                                6.27            14.12    8.20                                                 5.54            16.00    14.79                                                5.20            17.04    6.15                                                 4.66            19.04    7.18                                                 4.42            20.10    4.77                                                 4.06            21.88    18.19                                                3.87            22.96    62.64                                                3.68            24.20    49.94                                                3.56            25.00    32.96                                                3.45            25.82    100.00                                               3.38            26.36    73.67                                                3.24            27.52    25.20                                                3.06            29.16    26.81                                                2.98            30.02    19.04                                                2.88            31.04    8.96                                                 2.84            31.56    11.08                                                2.66            33.72    7.78                                                 2.60            34.52    8.70                                                 ______________________________________                                    

These data indicate longer times are necessary under these conditions tocomplete crystallization.

EXAMPLE 10

To water (47.2 g) was added sodium aluminate (1.075 g, technical grade,74% solids) and sodium hydroxide (0.518 g). This mixture was stirredbriefly to complete dissolution, then 1,4-diaminocyclohexane (.sup.˜ 80cis:20 trans) (5.532 g) was added. To this solution was added silica(Ultrasil™, 9.12 g), and the resulting gel was transferred to a Teflon™liner, placed in an autoclave, pressurized (100 psig), sealed, thenheated (145° C.) with stirring (.sup.˜ 350 rpm) for 8 days. Aftercooling, the product was suction filtered, washed with water, then dried(110° C., in vacuo) to give ZSM-35 as a white powder (9.06 g). The XRDpattern (lambda=1.5418) of the product is set out in Table 10.

                  TABLE 11                                                        ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        19.30           4.58     20.22                                                15.38           5.74     7.87                                                 12.08           7.31     13.80                                                11.10           7.96     22.06                                                9.36            9.44     100.00                                               7.66            11.54    3.56                                                 6.98            12.67    32.07                                                6.49            13.63    15.60                                                6.10            14.52    4.12                                                 5.62            15.76    17.46                                                4.89            18.14    7.62                                                 4.21            21.08    14.46                                                4.04            21.96    45.38                                                3.94            22.52    54.05                                                3.73            23.81    36.66                                                3.61            24.62    17.30                                                3.51            25.38    89.29                                                3.43            25.98    50.37                                                3.29            27.11    27.40                                                3.10            28.80    17.68                                                3.02            29.57    12.43                                                2.92            30.57    6.99                                                 2.86            31.22    9.89                                                 2.67            33.55    5.99                                                 2.63            34.12    8.74                                                 2.56            34.94    5.48                                                 ______________________________________                                    

EXAMPLE 11

To water (47.2 g) was added sodium hydroxide (1.051 g). This mixture wasstirred briefly to complete dissolution, then 1,4-diaminocyclohexane(.sup.˜ 80 cis:20 trans) (5.548 g) was added. To this solution was addedsilica (Ultrasil™, 9.13 g), and the resulting gel was transferred to aTeflon™ placed in an autoclave, pressurized (100 psig), sealed, thenheated (145° C.) with stirring (.sup.˜350 rpm) for 8 days. Aftercooling, the product was suction filtered, washed with water, then dried(110° C., in vacuo) to give a white powder (7.4o g). The XRD pattern(lambda=1.5418) of the product is set out in Table 11.

                  TABLE 12                                                        ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        19.35           4.56     10.05                                                15.12           5.84     100.00                                               9.86            8.96     2.13                                                 7.62            11.60    6.80                                                 5.10            17.36    8.60                                                 4.27            20.80    15.18                                                4.07            21.84    59.39                                                3.64            24.44    7.40                                                 3.55            25.08    8.23                                                 3.44            25.88    21.86                                                3.33            26.76    17.98                                                3.14            28.40    18.87                                                2.93            30.48    3.27                                                 2.81            31.80    4.13                                                 2.62            34.20    2.53                                                 ______________________________________                                    

After calcining (500° C., 2 hrs.) a portion of the above product the XRDpattern of Table 13 was obtained:

                  TABLE 13                                                        ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        12.13           7.28     6.96                                                 9.28            9.52     3.84                                                 4.22            21.04    26.60                                                4.06            21.88    100.00                                               3.32            26.84    32.15                                                ______________________________________                                    

EXAMPLE 12

To water (47.2 g) was added sodium aluminate (1.440 g, technical grade,74% solids) and sodium hydroxide (1.536 g). This mixture was stirredbriefly to complete dissolution, then 1,4-diaminocyclohexane (.sup.˜ 80cis:20 trans) (2.253 g) was added. To this solution was added silica(Ultrasil™, 9.12 g), and the resulting gel was transferred to a Teflon™liner, placed in an autoclave, pressurized (100 psig), sealed, thenheated (145° C.) with stirring (.sup.˜ 350 rpm) for 8 days. Aftercooling, the product was suction filtered, washed with water, then dried(110° C., in vacuo) to give ZSM-35 as a white powder (8.60 g). The XRDpattern (lambda=1.5418) of the product is set out in Table 11.

                  TABLE 14                                                        ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        11.15           7.92     18.84                                                9.36            9.44     100.00                                               7.02            12.60    32.31                                                6.87            12.88    16.80                                                6.54            13.52    16.36                                                ______________________________________                                    

EXAMPLE 13

To water (47.2 g) was added sodium aluminate (0.793 g, technical grade,74% solids) and sodium hydroxide (0.75 g). This mixture was stirredbriefly to complete dissolution, then 1,4-diaminocyclohexane (.sup.˜ 80cis:20 trans) (5.563 g) was added. To this solution was added silica(Ultrasil™, 9.27 g), and the resulting gel was transferred to a Teflon™liner, placed in an autoclave, pressurized (100 psig), sealed, thenheated (145° C.) with stirring (.sup.˜ 350 rpm) for 8 days. Aftercooling, the product was suction filtered, washed with water, then dried(110° C., in vacuo) to give a white powder (8.60 g). The XRD pattern(lambda=1.5418) of the product is set out in Table 15.

                  TABLE 15                                                        ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        11.33           7.80     14.17                                                9.53            9.28     82.58                                                7.06            12.54    21.40                                                6.58            13.46    11.08                                                5.72            15.50    15.77                                                4.91            18.08    8.59                                                 4.29            20.70    26.97                                                4.08            21.78    100.00                                               3.99            22.30    63.09                                                3.78            23.54    37.27                                                3.65            24.42    21.29                                                3.54            25.18    72.09                                                3.46            25.74    45.38                                                3.34            26.68    26.56                                                3.13            28.54    19.39                                                3.04            29.38    13.67                                                2.88            31.02    10.13                                                ______________________________________                                    

After calcining (538° C., 3 hrs.) a portion of the above productdisplayed the XRD pattern set out in Table 16.

                  TABLE 16                                                        ______________________________________                                        Interplanar     Degrees  Relative                                             d-Spacing (A)   2-Theta  Intensity                                            ______________________________________                                        9.01            9.82     78.98                                                6.77            13.08    27.56                                                6.41            13.82    14.31                                                6.40            13.84    14.31                                                5.53            16.02    13.95                                                4.60            19.30    9.41                                                 4.20            21.14    32.63                                                4.01            22.18    100.00                                               3.89            22.88    62.41                                                3.70            24.06    35.66                                                3.60            24.76    21.26                                                3.46            25.76    48.96                                                3.41            26.16    39.15                                                3.30            27.04    35.01                                                3.08            28.96    24.29                                                2.99            29.86    18.98                                                2.90            30.84    11.79                                                2.84            31.48    12.19                                                2.60            34.50    9.193                                                ______________________________________                                    

                  TABLE 17                                                        ______________________________________                                        INGREDIENT RATIOS AND REACTION                                                TEMPERATURES FOR ZSM-35 SYNTHESIS                                                  Directing                                                                     Agent    SiO.sub.2 /                                                                            OH/  H.sub.2 O/                                                                          Na/  R/   Rxn                               Ex.  (R)      Al.sub.2 O.sub.3                                                                       SiO.sub.2                                                                          SiO.sub.2                                                                           SiO.sub.2                                                                          SiO.sub.2                                                                          Temp                              ______________________________________                                        1    T        21.49    0.00 19.06 0.20 0.34 145                               2    T        28.61    0.03 19.01 0.17 0.34 145                               3    T        28.6     0.03 19.02 0.18 0.35 145                               4    T        59.67    0.06 18.98 0.14 0.35 145                               5    T        59.53    0.09 18.94 0.17 0.34 145                               6    T        1745.14  0.18 18.91 0.19 0.34 145                               7    T        1745.14  0.19 18.91 0.20 0.35 100                               8    T        21.28    0.00 19.07 0.20 0.14 145                               9    T        102.17   0.08 18.94 0.12 0.34 145                               10   C/T      28.49    0.02 19.02 0.17 0.34 145                               11   C/T      1745.14  0.19 18.91 0.20 0.34 145                               12   C/T      21.35    0.00 19.07 0.20 0.14 145                               13   C/T      39.01    0.08 18.7  0.19 0.34 145                               ______________________________________                                         T = trans1,4-diaminocyclohexane                                               C/T = 80% cis/20% trans(1,4-diaminocyclohexane)                          

The calcined product of Example 13 is evaluated for sorption capacitiesand Alpha Value. It has an Alpha Value of 240 and the followingequilibrium adsorption capacities in grams/100 grams of zeolite:

    ______________________________________                                               H.sub.2 O                                                                              9.0                                                                  Cyclohexane                                                                            1.0                                                                  n-Hexane 5.4                                                           ______________________________________                                    

These examples demonstrate the present invention of synthesizing ZSM-35from the required reaction mixture having a low alkalinity, low YO₂ /X₂O₃ molar ratio and directing agent of 1,4-diaminocyclohexane. When theYO₂ /X₂ O₃ ratio in the reaction mixture is greater than about 50,something other than ZSM-35 forms. Synthesis conditions using a YO₂ /X₂O₃, e.g., SiO₂ /Al₂ O₃, , ratio at about 70 produced a layered material.Synthesis conditions using YO₂ /X₂ O₃, e.g., SiO₂ /Al₂ O₃, ratio near 20with an R/YO₂ ratio less than 0.18 produced a mixture of layered andamorphous material instead of crystalline ZSM-35.

Changes and modifications in the specifically described embodiments canbe carried out without departing from the scope of the invention whichis intended to be limited only by the scope of the appended claims.

What is claimed is:
 1. A method for synthesizing crystalline materialexhibiting a characteristic X-ray diffraction pattern includingd-spacing maxima values as shown in Table 1, which comprises (i)preparing a mixture capable of forming said material, said mixturecomprising sources of alkali or alkaline earth metal (M), an oxide oftrivalent element (X), an oxide of tetravalent element (Y), water anddirecting agent (R) of 1,4-diaminocyclohexane, and having a composition,in terms of mole ratios, within the following ranges:

    ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                         1 to 100                                                  H.sub.2 O/YO.sub.2  10 to 100                                                 OH.sup.- /YO.sub.2  0.001 to 0.25                                             M/YO.sub.2          0 to 2.0                                                  R/YO.sub.2          0.1 to 2.0                                                ______________________________________                                    

(ii) maintaining said mixture under sufficient conditions including atemperature of from about 100° C. to about 200° C. until crystals ofsaid material are formed; and (iii) recovering said crystalline materialfrom step (ii), said recovered crystalline material containing said R.2. The method of claim 1 wherein said mixture has the followingcomposition ranges:

    ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                   10 to 50                                                        H.sub.2 O/YO.sub.2                                                                          15 to 50                                                        OH.sup.- /YO.sub.2                                                                          0.001 to 0.1                                                    M/YO.sub.2    0.1 to 1.0                                                      R/YO.sub.2     0.1 to 1.0.                                                    ______________________________________                                    


3. The method of claim 1 wherein said mixture further comprises seedcrystals in sufficient amount to enhance synthesis of said crystallinematerial.
 4. The method of claim 3 wherein said seed crystals have thestructure of ZSM-
 35. 5. The method of claim 1 wherein said X isaluminum, boron, iron, gallium, indium or a mixture thereof, and said Yis silicon, germanium, tin or a mixture thereof.
 6. The method of claim1 wherein X comprises aluminum and Y comprises silicon.
 7. The method ofclaim 1 wherein R consists essentially of trans-1,4-diaminocyclohexane.8. A mixture capable of forming crystals of ZSM-35 structure uponcrystallization, said mixture comprising sources of alkali or alkalineearth metal (M), trivalent element (X) oxide selected from the groupconsisting of oxide of aluminum, boron, iron, gallium, indium andmixtures thereof; tetravalent element (Y) oxide selected from the groupconsisting of oxide of silicon, germanium, tin and mixtures thereof;water and directing agent (R) of 1,4-diaminocyclohexane, and having acomposition, in terms of mole ratios, within the following ranges:

    ______________________________________                                        YO.sub.2 /X.sub.2 O.sub.3                                                                    1 to 100                                                       H.sub.2 O/YO.sub.2                                                                           10 to 100                                                      OH.sup.- /YO.sub.2                                                                            0 to 0.25                                                     M/YO.sub.2      0 to 2.0                                                      R/YO.sub.2     0.1 to 2.0.                                                    ______________________________________                                    


9. The method of claim 1 comprising replacing ions of the crystallinematerial recovered in step (iii), at least in part, by ion exchange withan ion or a mixture of ions selected from the group consisting ofhydrogen and hydrogen precursors, rare earth metals and metals fromGroups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB and VIII of the PeriodicTable of Elements.
 10. The method of claim 2 comprising replacing ionsof the crystalline material recovered in step (iii), at least in part,by ion exchange with an ion or a mixture of ions selected from the groupconsisting of hydrogen and hydrogen precursors, rare earth metals andmetals from Groups IIA, IIIA, IVA, IB, IIB, IIIB, IVB, VIB and VIII ofthe Periodic Table of Elements.
 11. The method of claim 9 wherein saidreplacing ion is hydrogen or a hydrogen precursor.
 12. The method ofclaim 10 wherein said replacing ion is hydrogen or a hydrogen precursor.13. The recovered crystalline material of claim
 1. 14. The recoveredcrystalline material of claim
 2. 15. The R-containing productcrystalline material of claim
 9. 16. The R-containing productcrystalline material of claim
 10. 17. The R-containing productcrystalline material of claim
 11. 18. The R-containing productcrystalline material of claim 12.